Mordants for bleachable filter layers



MORDANTS FOR BLEACHABLE FILTER LAYERS Filed Aug. 16, 1965 FIG GELAT/NCONTAIN/N6 SALT OF DYE AND 3-LAUROYLAMINO -I-- (N, N DIME THYL 3*AMINO/PROP/OPHE NONE HYDRO- CHL ORIDE LIGHT-SENSITIVE SILVER HAL/DEEMULSION FILM SUPPORT LIGHT-SENSITIVE SILVER HAL/DE EMULSION DE LA TINCON TA/NING SAL T OF DYE AND 3-LAUROYLAMINO (IV, N-DIME TH )L- 3-AM/NO)PROPIOPHE NONE HYDRO CHL OR/DE FILM SUPPORT -BLUE-SENSITIVESILVER HAL/DE EMULSION GELATIN CONTAIN/N6 SALT OF DYE AND 3-LAUROYLAMINO-/-(N, N-DIME THYL- S-AM/NOIPROP/OPHE NONE HYDROCHLORIDEr-GREEN-SENS/T/VE SILVER HAL/DE EMULSION 2O PRED-SENSITIVE SILVER HAL/DEEMULSION 2/ L FILM SUPPORT DUG'ALD A. BROOKS INVENTOR.

BY Dam/M ATTORNEY 8 AGENT United States Patent MORDANTS FOR BLEACHABLEFILTER LAYERS Dugald A. Brooks, Rochester, N.Y., assignor to EastmanKodak Company, Rochester, N .Y., a corporation of New Jersey Filed Aug.16, 1965, Ser. No. 479,719

US. CI. 9684 Int. Cl. G03c 1/84 This invention relates to certain bulky,i.e., relatively high molecular weight, compounds that contain alkalicleavable, basic nitrogen groups such as alkylamino groups or nitrogenheterocyclic nuclei and function as alkalirelease mordants, tophotographic materials, and more particularly to photographic elementscontaining these compounds in light-screening and light-absorbinglayers, and to methods for their preparation.

The use of organic dye containing light-filter and lightabsorbing layersin photographic elements is well known as is the use of mordants whichform substantially insoluble salts or otherwise react with water-solubledyes, to render the dyes non-diffusing. Such dye-mordant lightscreeningsalt may be in a layer overlying a light-sensitive emulsion or overlyingtwo or more light-sensitive emulsions; or it may be in a light-sensitiveemulsion for the purpose of modifying a light record in such emulsion orfor protecting an overlying light-sensitive emulsion or emulsions fromthe action of light of wavelengths absorbed by such light-screeningsubstance, or it may be in a layer not containing a light-sensitivesubstance but arranged between two light-sensitive emulsions; or it maybe in a layer serving as a backing on an element having one or morelight-sensitive emulsions (for example, to reduce halation).

In particular, light-screening substances are often required (a) inovercoatings upon photographic elements to protect the light-sensitiveemulsion or emulsions from the action of light which it is not desiredto record, (b) in layers arranged between differentially colorsensitized emulsions, e.g., to protect redand green-sensitive emulsionsfrom the action of blue light, and (c) in backings forming the so-calledantihalation layers on either side of a transparent support carrying thelight-sensitive emulsion or emulsions.

In most cases and especially where the element contains a colorsensitized emulsion or color sensitized emulsions, it is particularlydesirable to employ light-screening substances which do not affect thegeneralsensitivity or the color sensitivity of light-sensitive emulsionswith which they may come into contact. It is also particularly desirableto employ light-screening substances which do not substantially diffusefrom the layers or coatings in which they are incorporated, eitherduring the manufacture of the element or on storing it or inphotographically processing it. Finally it is generally necessary toemploy light-screening substances which can readily be renderedineffective, i.e., decolorized or destroyed and removed prior to orduring or after photographic processing. For many purposes it isparticularly convenient to employ light-screening substances which arerendered ineffective by one of the photographic baths employed inprocessing the element after exposure, such as a photographic developingbath or fixing bath.

Numerous substances have been proposed as mordants to prepare thedye-mordant salts used as light-screening and light-absorbing materialsfor the purposes indicated above. Among the proposed mordants arerelatively high molecular weight compounds having ionic charges oppositeto those of the particular light-absorbing dye. For example, the dyeemployed might be an acid dye, in which case the mordant would becationic. Typical of such proposed anordants are, for example, derivedpolymers such Claims ice as the basic reaction products of thepolyvinylsulfonates and C-aminopyridines as described in D. D. Reynoldset al., US. Patents 2,701,243 and 2,768,078, granted Feb. 1, 1955, andOct. 23, 1956, respectively. While polymeric mordants such asillustrated by the above-mentioned patents have the advantage of bulkymolecules and do function to fix acid dyes in photographic layers,within their particular limitations, they have not been found entirelysatisfactory in many applications primarily because these polymericmordants on alkaline development do not tend to release the dye, stillretain their mordanting property and, accordingly, not only tend toretain some residual dye as evidenced by background stain or coloration,but more importantly retain, i.e., fix, an appreciable amount ofthiosulfate ion in the subsequent hypo processing used to removeunexposed silver halide. This results in relatively poor keepingqualities of the produced image. In view of this, it would be verydesirable to have an effective mordant available that is free from suchdisadvantages.

I have now found that certain bulky or relatively high molecular weightcompounds that contain alkali cleava'ble alkylamino groups or nitrogenheterocyclic nuclei are especially useful as precipitants and mordantsfor acid dyes in photographic layers, and that these compounds,moreover, satisfactorily overcome the above mentioned shortcomings ofheretofore known mordants for this purpose. Thus, when incorporated inphotographic layers, they function effectively as alkali-releasemordants without retention of any residual dye or deleterious amounts ofthiosulfate ion in the layers on processing, and the produced images areof very good quality and of outstanding keeping properties. Thesemordants are soluble in aqueous solutions, for example, dilute solutionsof acids such as acetic, butyric, lauric, etc. acids. Furthermore, theyreadily form substantially non-diifusible salts with watersoluble dyes,and these are all compatible with various hydrophilic materials such asgelatin. In general, they have a molecular weight of at least 300.

It is, accordingly, an object of the invention to provide a photographicelement having one or more layers containing at least one of the bulkybasic nitrogen groups containing compounds or salts of the inventiondescribed above. Another object is to provide a backing layer containingat least one of these salts. Another object is to provide a light filterlayer containing at least one of the above salts; which layer may becoated between two or more silver halide emulsion layers in a multilayerelement. Another object is to provide an imbibition blank containing atleast one of the above salts. Another object is to provide alight-sensitive gelatino-silver halide layer containing at least one ofthe above salts. Another object is to provide overcoating layers forphotographic elements which contain at least one of the above salts.Another object is to provide a process for preparing the bulky nitrogencompounds and salts thereof. Other objects will become apparent fromconsideration of the description and the examples.

The bulky compounds that contain alkali cleavable alkylamino groups ornitrogen heterocyclic nuclei that are useful in the invention asalkali-release mordants include those represented by the followingformula:

wherein n, g, and m each represent the same or different integers offrom 1 to 2; R represents a lower alkyl (e.g., methyl, ethyl, butyl,etc.), alkoxy (e.g., methoxy, propoxy, butoxy, etc.), aryl (e.g.,phenyl, tolyl, ethylphenyl, etc.), aryloxy (e.g., phenoxy, tolyloxy,ethylphenoxy, etc.), aralkyl (e.g., benzyl, phenethyl, etc.), etc.; Rand R each represent the same or different members, such as,

hydrogen, an alkyl group having typically from 1 to 20 carbon atoms(e.g., methyl, propyl, isopropyl, dodecyl, phytyl, benzyl, phenethyl,etc.) or an aryl group (e.g., phenyl, dodecylphenyl, biphenyl,decyloxyphenyl, benzylphenyl, phenoxyphenyl, halophenyl, naphthyl,etc.); R represents an alkyl group having from 1 to 20 carbon atoms asdescribed for R and an aryl group (e.g., phenyl, tolyl, octadecylphenyl,methoxyphenyl, dodecoxyphenyl, diphenyl, naphthyl, benzylphenyl,phenoxyphenyl, acetaminophenyl, propion-aminophenyl, laurylaminophenyletc.); when n and g each represent the integer 1, R and R taken togetherrepresent a divalent alkylene group having from 3 to 4 carbon atoms inthe chain and having the formula:

wherein i represents an integer of from 3 to 4; R represents hydrogen,an alkyl group having from 1 to 20 carbon atoms (e.g., methyl, decyl,octadecyl, phytyl, benzyl, tolylmethyl, phenethyl, etc.), and aryl(e.g., phenyl, tolyl, decylphenyl, octadecyloxyphenyl, =benzylpheny1,biphenyl, phenoxyphenyl, halophenyl, naphthyl, etc.); when m representsthe integer 2, A represents a bifunctional group in which each of saidfunctional groups is a substituted nitrogen atom having a valence withan odd number of from 3 to 5 with none of said substituents attached tothe nitrogen being hydrogen, and when said nitrogen atom has a valenceof 5, one of said substituents wherein R represents a lower alkyl group(e.g. methyl, ethyl, butyl, etc.); d represents an integer of from 2 to6; X represents an acid anion (e.g., chloride, bromide, iodide,thiocyanate, sulfamate, perchlorate, methyl sulfate, ethyl sulfate,p-toluenesulfonate, etc.), and when m represents the integer 1, Arepresents a monofunctional group,

wherein R R and R each represent the same or different alkyl group(e.g., methyl, ethyl, decyl, etc.), and R and R taken together representthe nonmetallic atoms required to complete a 6-membered saturatedheterocyclic nucleus (e.g., piperidino, morpholino, and N-su-bstitutedpiperazino (e.g., N-methylpiperazino, N-butylpiperizino,N-phenylpiperizino, etc.), X is as defined previously; R representshydrogen, or a lower alkyl group (e.g., methyl, ethyl, etc.), each ofsaid A groups having a molecular weight of less than 300; whenmonofunctional and less than 150 when bifunctional, Z represents thenonmetallic atoms required to complete an imidazoline nucleus; and Zrepresents the nonmetallic atoms required to complete a nucleuscontaining a heterocyclic ring having from 5 to 6 atoms, typical heteroatoms being nitrogen, oxygen, sulfur and selenium, Z representingparticularly a thiazoline nucleus e. g., thiazoline, 4-methylthiazoline,4-phenylthiazoline, S-methylthiazoline, S-phenylthiazoline,4,5-dimethylthiazoline, 4,5-diphenylthiazoline,

4- (Z-thienyl) -thiazoline, etc.

a benzothiazoline nucleus (e.g., benzothiazoline,4-chlorobenzothiazoline, S-chlorobenzothiazoline,-chlorobenzothiazoline, 7-chlorobenzothiazoline,4-methylbenzothiazoline, S-methylbenzothiazoline,6-methylbenzothiazoline, 5-bromobenzothiazoline, 6-bromobenzothiazoline,4-phenylbenzolthiazoline, S-phenylbenzothiazoline,4-methoxybenzothiazoline, 5-methoxybenzothiazoline,6-methoxybenzothiazoline, S-iodobenzothiazoline, 6-iodobenzothiazoline,4-ethoxybenzothiazoline, S-ethoxybenzothiazoline,tetrahydrobenzothiazoline, 5,6-dimethoxybenzothiazoline,5,6-dioxymethylenebenzothiazoline, 5-hydroxybenzothiazoline,6-hydroxybenzothiazoline, etc.), a naphthothiazoline nucleus e. g.,a-naphthothiazoline, ,B-naphthothiazoline,S-methoxy-fi-naphthothiazoline, S-ethoxy-B-naphthothiazoline,7-methoxy-a-naphthothiazoline, 8-methoXy-a-naphthothiazoline, etc. athianaphtheno-7,6',4,S-thiazoline nucleus (e.g.,4'-methoXythianaphtheno-7',6',4,S-thiazoline, etc.), an oxazolinenucleus (e.g., 4-methylox-azoline, S-methyloxazoline, 4-phenyloxazoline,4,5-diphenyloxazoline, 4-ethyloxazoline, 4,5-dimethyloxazoline,

5 -phenyloxazo1ine, etc.

a rbenzoxazoline nucleus (e.g., benzoxazoline, S-chlorobenzoxazoline,S-methylbenzoxazoline, S-phenylbenzoxazoline, 6-methylbenzoxazoline,5,6-dimethylbenzoxazoline, 4,6-dimethylbenzoxazoline,S-methoxybenzoxazoline, S-ethoxybenzoxazoline, 6-chlorobenzoxazoline,6-methoxybenzoxazoline, S-hydroxybenzoxazoline, 6-hydroxybenzoxazoline,etc.) a naphthoxazoline nucleus (e.g., a-n'aphthoxazoline,,B,5-naphthoxazoline, ,B-naphthoxazoline, etc.-),

a selenazoline nucleus (e.g., 4-methylselenazoline,4-phenylselenazoline, etc.),

a benzoselenazoline nucleus (e.g., benzoselenazoline,5-chloroselenazoline, S-methoxyhenzoselenazoline,S-hydroxybenzoselen'azoline, tetrahydrobenzoselenazoline, etc. anaphthoselenazoline nucleus (e.g., a-naphthoselenazoline,5,;3-naphthoselenazoline, fl-naphthoselen azoline, etc.

a thiazoline nucleus (e.g., thiazoline,

4-methylthiazoline, etc.), a 1,2,3,4-tetrahydroisoquinoline nucleus(e.g., l,2,3,4-tetrahydroisoquinoline,S-methyl-l,2,3,4-tetnahydroisoquinoline,S-methyl-1,2,3,4-tetrahydroisoquinoline,6-chloro-1,2,3,4-tetrahydroisoquinoline,6-methoxy-1,2,3,4-tetrahydroisoquinoline,8-hydroxy-l,2,3,4-tetrahydroisoquinoline, etc.), a 3,3-dialkylindoleninenucleus (e.g., 3,3-dimethylindolenine, 3,3,5-trimethylindolenine,3,3,7-trimethylindolenine, etc. a l-substituted imidazoline nucleus(e.g., l-alkylimidazoline, 1-alkyl-4-phenylimidazoline,1-alkyl-4,S-dimethylimidazoline, etc.), a l-substituted benzimidazolinenucleus (e.g., l-alkylbenzimidazoline,1-aryl-5,6-dichlorobenzimidazoline, etc.), a l-substitutednaphthimidazoline nucleus (e.g., 1-alkyl-u-naphthimidazoline,1-aryl-fi-naphthimidazoline, 1-alkyl-5-methoxy-wnaphthimidazoline,etc.), a 1,2,4-thiadiazoline nucleus, a lor 4-alkyl-1,2,4-triazolinenucleus (e.g. l-methyl-1,2,4-triazoline, 1-butyl-1,2,4-triazoline,4-ethyl-1,2,4-triazoline, etc.), a tetrazoline nucleus (e.g.tetrazoline, S-methyl-1,2,3,4-tetrazoline, 5-phenyl-1,2,3,4-tetrazoline,etc. and the like nuclei.

The components of Formula I above are so chosen as to give compoundshaving molecular weights in each instance of at least 150 for compoundsderived from di-amines and 300 for compounds derived from monofunctionalamines. Preferably, the compounds containing the -NR R groups are usedin the form of their salts (e.g., the hydrochloride, the acetate, etc.)or in their quaternized forms, i.e., containing the group 5 -NR X\R1wherein X, R R and R are as previously defined.

Included among the preferred mordants of Formula I are those having theformulas:

wherein p represents an integer of from 1 to 3, R R R R R and X are asdefined previously and R represents the hydrogen atom, a straight orbranched chain al-kyl group of from 1 to 22 carbon atoms (e.g., methyl,ethyl, propyl, isopropyl, butyl, hexyl, dodecyl, octadecyl, etc.), anaryl group (e.g., phenyl, tolyl, naphthyl, etc.), an aralkyl group(e.g., benzyl, phenethyl, etc.), an alkoxy group (e.g., methoxy, ethoxy,butoxy, etc.) an aryloxy group (e.g., phenoxy, tolyloxy, naphthoxy,etc.), an alkoxyalkyl group (e.g., methoxymethyl, ethoxybutyl,isopropoxybutyl, butoxydodecyl, etc.), an acylamino group (e.g.,acetamino, propionamino, butyrylamino, la-uroylamino, etc.).

In general my mordants of Formula I are produced by a Mannich reactionin which a ketone having the formula:

IV 0 O R. R1

R. O..tNH .-t( GH=t),. a.. in which R, R R 11 and g are as definedpreviously, is reacted with an aldehyde having the formula:

in which R is as defined previously and an amine (or amine salt) havingone of the formulas;

wherein R R R X and a are as defined previously or XL Z R;HdI I-R inwhich R and Z have been defined previously and R represents an alkylgroup having from 1 to 4 carbon atoms.

The mordants of Formula I in which m is 1 are produced advantageously byreacting compounds of Formulas IV, V, and VI or XI in mole ratios ofabout 1:1:1 respectively, while the compounds in which m is 2 areproduced advantageously by reacting compounds of Formulas IV, V, and VIIand VIII or IX or X in mole ratios of about 2:2:1 respectively.

The immediate reactions are advantageously carried out in a solvent suchas glacial acetic acid and preferably at an elevated tmeperature, forexample on a steam bath for several hours, the product then beingprecipitated by adding a nonsolvent (e.g., acetone), filtered out andrecrystallized, for example, from absolute ethyl alcoholethyl acetatemixture. These compounds of Formula I may be quaternized by heating witha suitable quaternizing agent R7X wherein R and X are as previouslydefined (e.g., an alkyl halide, dialkyl sulfate, etc.) and thesecompounds are also effective alkali release mordants of the invention.

Illustrative ketones used to advantage include the following typicalexamples:

acetophenone lauroylaminoacetophenone decyl phenyl ketone ethyl phenylketone phenoxymethyl phenyl ketone phenethyl phenyl ketone benzyl phenylketone Z-butanone 2-octadecanone l-phenyl-octadecanone 2-phenylcyclohexanone Z-benzyl cyclohexanone 2-octadecyl cyclohexanone 2-phenylcyclopentanone 2-phytyl cyclopentanone Illustrative aldehydes used toadvantage include formaldehyde, paraformaldehyde, acetaldchyde,benzaldehyde, etc.

Any monofunctional primary or secondary amine having a molecular weightof less than 300 or a bifunctional primary or secondary amine having amolecular weight of less than 150 can be used to advantage. Typicalmonofunctional amines includes the following:

aniline N-methylamine N-octadecylamine N,N-dibutylamineN,N-dimethylarnine N-methylaniline N-methylpiperazine morpholinepiperidine thiazoline 1,2,3,4-tetrahydroisoquinoline Typicalbifunctional amines include the following:

N,N'-dimethylpentamethylenedianiine N,N-dimethylethylenediamineimidazoline The following compounds will still further illustrate themordants of Formula I.

Mordant No.: Name 1 3 lauroylamino 1 (N,N-dimcthyl-3- amino)propiophenone hydrochloride.

2 3 lauroylamino-l-(N,N,N-trimethyl-3- ammonium)propiophenone iodide.

3 3 dodecylphenylcarbamylcarbonylethyl-N,N-dimethylamine hydrochloride.

4 3 dodecylphenylcarbamylcarbonylethyl-N,N,Nirimethylammonium iodide.

5 3 laurylbenzoylethyl N,N dimethylamine hydrochloride.

6 3 laurylbenzoylethyl N,N,N trimcthylammoniurn iodide.

7 3 laurylbenzoylethyl N morpholine hydrochloride.

8 3 laurylbenzoylethyl N methyl N- morpholiniurn iodide.

9 1,4 bis(3 laurylbenzoylethyl)piperazine dihydrochloride.

10 1,4 bis(3 laurylbenzoylethyl)N,N'-dimethylpiperazinium diiodide.

11 3 decylbenzoylethylpiperidine hydrochloride.

12 3 decylbenzoylethyl N-methylpiperidinium iodide.

13 6 (N,N dimethylaminomethyl) 2- laurylcyclohexane hydrochloride.

14 6 (N,N,N,N tetramethylamrnonium)- 2-laurylcyclohexane iodide.

15 3 laurylbenzoyl 1 butenyl N,N-

dimethylarnine hydrochloride.

16 3 laurylbenzoyl 1 butenyl N,N,N-

trimethylammonium iodide.

17 3 laurylbenzoyl 3 butyl N,N dimethylamine hydrochloride.

1g 3 laurylbenzoyl 3 butyl N,N,N-trimethylammonium iodide.

19 3 octadecylbenzoyl 2 isopropyl-N,N-

dimethylamine hydrochloride.

20 3 octadecylbenzoyl-Z-isopropyl-N,N,N

trimethylammonium iodide.

21 3 phytylbenzoyl 1,2 diphenylethyl- N,N-dimethylarnine hydrochloride.

22 3 phytylbenzoyl 1,2 diphenylethyl- N,N,N-trimethylammonium iodide.

23 N methyl N,N bis(3 laurylbcnzoylethyl)amine hydrochloride.

24 N,N dimethyl N,N bis(3 laurylbenzoylethyl)ammonium iodide.

25 1,5 bis(3 laurylbenzoylcthyl) N,N- dimethylpentamethylene diaminedihydrochloride.

26 1,5 bis(3 laurylbenzoylethyl) N,N,

N,N' tetramethyl diammonium diiodide.

27 3 (3 laurylbenzoylethyl)benzothiazoline hydrochloride.

28 3 (3 laurylbenzoylethyl)benzothiazolinium iodide.

29 1,3 di(3 laurylbenzoylethyl)benzimidazoline dihydrochloride.

30 1,3 di(3 laurylbenzoylethyl)benzimidazolinium diiodide.

31 Phytyloylethyl N,N dimethylamine hydrochloride.

32 Phytyloylethyl N,N,N trimethylammonium iodide.

As previously mentioned, the above-defined mordants of the inventionfunction as alkali-release mordants in photographic layers. Thus, underappropriate conditions of pH (i.e., alkaline conditions), they decomposeto split or cleave the basic nitrogen fragment off of the bulky residue,and to lose their ability to act as mordants with release and subsequentremoval of the mordanted dye from the system. A major advantage of theabove alkalirelease mordants is, therefore, that the compounds do notretain either the previously mordanted dye or thiosulfate ion from thefixing bath, after processing, as do other compounds of similarmordanting ability.

The alkali cleavage reaction is illustrated with the structure ofFormula IX above as follows:

wherein 12, R R R R and X are as previously defined.

The invention is further illustrated by the following examplesdescribing the preparation and use of the mordanting compounds of theinvention in photographic layers and elements.

Example 1.3-lauroylamino-1-(N,N-dimethyl-3- amino)propiophenonehydrochloride A mixture of 10 g. 3-1aurolya1ninoacetophenone (0.031mole), 3.6 g. dimethylamine hydrochloride (0.044 mole), 2.5 g.paraformaldehyde (0.028 mole) in ml. glacial acetic acid was warmed on asteam bath for 3 hours. The dark red reaction mixture was reduced involume under reduced pressure. Acetone was added to the concentratedsolution. The resulting precipitate was collected and recrystallizedfrom absolute ethanol-ethyl acetate, M.P. 1624.5 C.

The intermediate 3-1auroy1aminoacetophenone in the above reaction wasprepared as follows:

A mixture of 20.0 g. m-aminoacetophenone (0.148 mole), approximately 10g. sodium hydroxide and 200 ml. water was treated dropwise with 32.4 g.lauroyl chloride (0.148 mole) at room temperature. The resultingreaction mixture assumed a wax-like consistency. It was filtered andwashed with water. The filtrate was neutralized with 6 N hydrochloricacid and the resulting solid collected. The collected portions werecombined and dried, then recrystallized from benzene. The product wasobtained as a white crystalline material, M.P. 87-895 C.

The above compound 3-lauroylamino-1-(N,N-dimethyl- 3-amino)propiophenonehydrochloride is an alkali cleavable Mannich base which can bedecomposed in alkali splitting the basic nitrogen fragement off of thebulky residue. This compound, at a ratio of parts by weight to 1 part byweight of dye, mordanted the dye bis [3- methyLl-p-sulfophenyl 2pyrazolin-5-one-(4)] pentamethineoxonol, in gelatin at a pH of 5.0, withno bleeding upon washing in water. The mordanted dye was partiallybleached upon treatment of the coated gelatin layer (on a celluloseacetate film support) with a photographic developer having thecomposition:

p-Methylaminophenol sulfate g. 4.5

Sodium sulfite, desiccated g. 90.0 Hydroquinone g. 8.0 Sodium carbonate,monohydrated g. 52.5 Potassium bromide g. 5.0 WaterTo make liters 1.0

The bleaching was increased when the alkalinity of the developer wasincreased by the addition of sodium hydroxide. The residual yellow colorwas discharged by subsequent acidification of the gelatin layer. Thiswas 10 mined, but none of the above samples bleached under theseconditions. Thiosulfate retention values were determined by theRoss-Crabtree Method on unexposed film coatings, processed in acommercial Recordak processing machine.

EXAMPLE 2 Similar results are obtained by substituting for mordant No. 1in Example 1 any of the specific illustrative mordants describedpreviously herein. In each instance the dye being mordanted is heldsecurely in its coated layer but upon photographic processing in thealkaline processing solutions the dye is completely released from thelayer. The fragments into which the mordant is cleaved by alkali are notcapable of and do not retain any dye or any thiosulfate ion in theprocessed photographic element.

The other odd-numbered mordants used to illustrate my invention areadvantageously prepared by the Mannich condensation by processes Wellknown in .the art. Table 1 lists the ketone, aldehyde and amine saltused to make the mordants. Unless otherwise indicated, approximatelyequimolar amounts are used. The even-numbered mordants are made from thepreceding odd-numbered mordants by treating it with methyl iodide.

Molrzdant Ketone Aldehyde Amine 3 Methyl3-dodecyl-1- IaraiormaldehydeDimethylamine hydrocarbamylphenyl ketone. chloride. 5 Methyl3laurylphenyl ketone .do Do. I 7 "do do Morpholine hydrochloride. 9Meghyl ii-laurylphenyl ketone Paratormaldehyde (2 moles) Piperazilnfdihydrochloride mo 8S [1 I110 B 11 Methyl 3decylphenul ketoneParaiormaldehyde Piperldine hydrochloride. 13 2-laurylcyclohexanone doDimetliiylarnine hydrochlor de. 15 Allyl 3-la;urylphenyl ketone do Do.17 Propyl 3-laurylphenyl ketone do Do. 19 Mletltiyl3-octadecylphenylAeetaldehyde Do.

'e one. 21 Benzyl S-phytylphenyl ketone. Benzaldehyde Do. 23 Methyl3-laurylphenyl ketone Paraiormaldehyde (2 moles) Methylamine hydroe (2moles). chloride (1 m e 25 do ..do 1.5-dimethyl pentamethylene diamine.27 Methyl 3-laurylphenyl ketone... Paralonnaldohyde Benzothiazolinehydrochloride. 29 Methyl 3-laurylphenyl ketone Paraformaldehyde (2moles) Benzimidazoline dihydro- (2 moles). chloride (1 mole). 31 Methylphytylketone Paraformaldehyde Dimethylamine'hydro' chloride.

then treated with a fixing bath of the following com 45 Still moretypical mordants of my invention are the position: following: ithlosulfate MO -dam; N NaIne si deslccated 48 336-(N,Ndimethylaminornethyl)-2-phenyl- Aceilc s 2 i 7 5 r cyclohexanonehydrochloride, Bone acid, crystals 00 346-(N,N-diethylarninomethyl)-2-tolyl-cyc1o- Potasslum 211ml t '0 hexanonehydrochloride. WateF-T0 ma 6 11 35 N,N-dibutylaminomethylcyclopentanoneResult:Mordanted well. Bleached effectively in the hydrochlor de.

developer. Retained no hypo from the fixing bath. 36 -p y y The aboveresults for Example 1 were made for hand 55 ethyl)hydrochloride.

coatings on cellulose acetate film support, the melts for which wereprepared as follows:

To 10 cc. of 10% photographic gelatin melted at 40 C. was added 30 orrngs. of mordant dissolved in 10 cc. of the appropriate solvent. The pHof the solution was adjusted to 4.5-5.0 with glacial acetic acid. Tothis was then added 10 mgs. of bis[3-methyl-l-p-shlfophenyl-S-pyraZolone-(4)]pentamethineoxonol dissolved in the appropr-iate solventwith vigorous stirring. The pH of the melt was then readjusted to 6.0 01with.2.5 N NaOH, a coating aid added, the total volume adjusted to 32cc. with distilled water and the melt coated and dried.

The bleed test consisted of immersinga portion of the hand coating instagnant, distilled water at 75 F. for 2 minutes and inspecting forsigns of dye bleeding out of the gel layer. If no bleeding was detected,the immersion was repeated for another 2 minute interval. Bleachabilitywas determined by immersing a portion of the hand coating in thedeveloper for 2 minutes and observing the loss in color. Bleachabilityin the fixing bath was also deter- These and the other mordants of myinvention are prepared according to the procedures described previously.Blicke in Chapter 10 of Organic Reactions, Volume 1, published by Wiley,describes the Mannich condensation reaction.

The photographic elements prepared with the abovedescribed mordants ofthe invention comprise a support material having thereon at least onehydrophilic colloid layer containing a mordant of the invention, whichlayer may also contain a light-sensitive silver halide. However, thepreferred light-sensitive photographic elements, comprise a supporthaving thereon at least one hydrophilic colloid layer containing amordant of the invention and at least one light sensitive silver halideemulsionlayer. The mordant containing light-screening and antihalationlayers are customarily prepared by coating on the support orphotographic elements by methods well known in the art, a water solutioncomprising at least one mordant of the invention, an acid dye, awater-permeable hydrophilic colloid binder and a coating aid such assaponin. For most purposes, it is also desirable to add agents to hardenthe colloidal binder material so that the light-screening layer willremain intact in the photographic element during and following theprocessing operations. The pH of the coating solution is adjusted whennecessary to a level that is compatible with the light-sensitiveemulsion layer by the usual methods. The proportions of mordant, dye,colloidal binder, hardener and coating aid may be varied over wideranges and will depend upon the specific requirement of the photographicelement being produced. The methods used to determine the optimumcompositions are well known in the art and require no furtherelucidation here. Suitable support materials include any of those usedin photography such as cellulose acetate, cellulose propionate,cellulose acetate-butyrate, cellulose nitrate, synthetic resins such asnylon, polyesters, polystyrene, polypropylene, etc., paper, and thelike.

Suitable hydrophilic colloid materials that can be used in the mordantcontaining compositions and layers, and photographic elements, of theinvention include gelatin, albumin, collodion, gum arabic, agar-agar,cellulose derivatives such as alkyl esters of carboxylated cellulose,hydroxy ethyl cellulose, carboxy methyl hydroxy ethyl cellulose,synthetic resins, such as the amphoteric copolymers described by Clavieret al. in U.S. Patent 2,949,442, issued Aug. 16, 1960, polyvinylalcohol, polyvinyl pyrrolidone, and others well known in the art. Theabove-mentioned amphoteric copolymers are made by polymerizing themonomer having the formula:

| COOH wherein R has the above-mentioned meaning, such as an alkylaminesalt. These monomers can further be polymerized with a third unsaturatedmonomer in an amount up to about 20%, and preferably from -15%, of thetotal weight of monomer used, such as an ethylene monomer that iscopolymerizable with the two principal monomers. The third monomer maycontain either a basic group or an acid group and may, for example, bevinyl acetate, vinyl chloride, acrylonitrile, methacrylonitrile,styrene, acrylates, methacrylates, acrylamide, methacrylamide, etc.Examples of these polymeric gelatin substitutes are copolymers ofallylamine and methacrylic acid; copolymers of allylamine, acrylic acidand acrylamide; hydrolyzed copolymers of allylamine, methacrylic acidand vinyl acetate; the copolymers of allylamine, acrylic acid andstyrene; the copolymers of allylamine, methacrylic acid andacrylonitrile; etc.

The dyes that can be effectively mordanted in accordance with myinvention include any filter dye that has one or more acidic groupsubstituents such as sulfo or carboxyl groups, including for example,the oxonol dyes described and claimed in copending application of JosephBailey, Ser. No. 98,709, filed Mar. 27, 1961, now Patent No. 3,247,127;having the formula:

and more particularly the dyes of the formula:

12 wherein Z represents the nonmetallic :atoms necessary to complete a1-carboxyalkyl-3-hydrocarbon substitutedhexahydro-2,4,6-trioxo-5-pyrimidine nucleus, n in each case is aninteger of from 1 to 3, each R represents a carboxy- -alkyl group inwhich the carboxy substituent is attached to an :alkyl group having from1 to 2 carbon atoms, R is an alkyl group of from 1 to 8 carbon atoms oran aryl group such as phenyl or an alkyl or alk-oxy substituted phenylgroup, and X is hydrogen or an alkyl group of from 1 to 4 carbon atoms,such that no more than one X" is an alkyl group. Other suitable aciddyes include the benzoxazole-pyrazolone merocyanine dyes described incopending application of Jones et al. U.S. Ser. No. 167,666, filed Jan.22, 1962, now Patent No. 3,282,699, having the formula:

wherein R represents :an alkyl group such as methyl, ethyl, propyl,isopropyl, butyl, isobutyl, tertiary butyl, etc., or a carboxyalkylgroup, such as carboxymethyl, carboxyethyl, carboxypropyl, etc., or asulfoalkyl group, such as sulfoethyl, sulfopropyl, sulfobutyl, etc.; Zrepresents the nonmetallic atoms necessary to complete a heterocyclicnucleus of the benzoxazole series (including benzoxazole and benzoxazolesubstituted with substitutions such as methyl, ethyl, phenyl, methoxy,ethoxy, chlorine, bromine, etc.) or a nucleus of the benzoxazole serieswhich has a sulfo-substituent on the benzene ring as well as one or moreof the above-mentioned simple substituents, such that when R representsan alkyl group, Z" represents the sulfo-substituted benzoxazole nucleusand when R, represents a carboxyalkyl group or a sulfoalkyl group, Z"represents the nonmetallic atoms necessary to complete a benzoxazolenucleus; Q represents the nonmetallic atoms necessary to complete aheterocyclic nucleus of the suitephenyl pyrazolinone series and n is aninteger from 1 to 3. However, the invention is not limited to just thosedyes coming within the general formulas of the above-mentioned copendingapplications, since as previously set forth any filter dye containingone or more sulfo or carboxyl groups can be employed, for example, theyellow dyes mentioned in Mader et al. U.S. Patent 3,016,306, issued Jan.9, 1962, columns 5 and 6.

Typical light-filtering dyes include, for example,

bis( 1-butyl-3 -carboxymethylhexahydro-2,4,6-trioxo-5- pyrimidinepentamethineoxonol,

bis( 1-carboxymethyl-3-cyclohexylhexahydro-2,4,6-trioxo- 5 pyrimidinepentamethineoxonol,

bis 1-butyl-3-carboxymethylhexahydro-2,4,6-triox0-S pyrimidine)trimethineoxonol,

bis( 1-carboxymethylhexahydro-3 -octyl-2,4,6-trioxo-S- pyrimidine)met-hineoxonol,

4-[ (3-ethyl-2 3H -benzoxazolylidine ethylidene] -3 methyl- 1-p-sulfophenyl) -2-pyrazolin-5-one monosulfonated,

4- 4- (3 -ethyl-2 3H -benzoxazoylidene) -2-butenylidene] 3-methyl-1-(p-sulfophenyl) -2-pyrazolin-5-one monosulfonated,

4[ (3-B-carboxyethyl-2 3H -benzox azolylidene ethylidene] -3-methyl- 1-p-sulfophenyl -2-pyrazolin-5-one,

4- [4- (3 -fi-carboxyethyl-2 (3H) -benzoxazolylidene)-2- butenylidene]-3-methyll- (p-sulfophenyl) -2-pyrazolin- S-one,

bis(1-butyl-3 -carboxymethyl-S-barbituric acid) trimethine oxonol,

bis(1-butyl-3 -carboxymethyl-S-barbituric acid pent-amethineoxonol,

bis 3-methyl- 1- (p-sulfophenyl) -2-pyrazolin-5-one (4) methineoxonol,

bis 3 -methyl-1- p-sulfophenyl -2-pyrazolin-5 -one (4) trimethineoxonol,

bis 3 -methyl-1- p-sulfophenyl -2-pyrazolin-5 -one-( 4)pentamethineoxonol,

bis 3-methyl-1- (p-sulfophenyl -5-pyrazolone-(4)] pentamethineoxonol,and

13 typical ultraviolet absorbing dyes include the 2,5-bis(substitutedsulfophenyl)thiazolo[5,4-d]thiazole disodium salts of Sawdey U .S. Ser.183,417 filed Mar. 29, 1962, such as 2,5 -bis o-methoxy-x-sulfophenylthiazolo ,4-d] thiazole disodium salt,

2,5-bis (o-hexyloxy-x-sulfophenyl)thiazolo[5,4-d]

thiazole disodium salt,

2,5-bis(o-decyloxy- -sulfophenyl)thiazolo[5,4-d] thiazole disodium salt,

2,5 -bis (o-methyl-x-sulfophenyl) thiazolo [5,4-d] thi-azole disodiumsalt,

2,5 -bis 5 -butyl-Z-methyl-x-sulfophenyl) thiazolo[5 ,4-d]

thiazole disodium salt,

2,5 -bis m-methyl-x-sulfo phenyl thiazolo [5 ,4-d] thiazole disodiumsalt,

2,5-bis p-propyl-x-sulfophenyl) thiazolo [5 ,4-d] thiazole disodiumsalt, etc.;

the ultraviolet absorbing dyes of Sawdey US. Patent 2,739,888, issuedMar. 27, 1956, such as3-phenyl-2-phenylimino-5-o-sulfobenzal-4-thiazolidone sodium salt,

5- 4-methoxy-3 -sulfob enzal -3 -phenyl-2-phenylimino-4- thiazolidone(sodium salt),

3-phenyl-2-phenylimino-5-[3-(3-sulfobenzamido)benza1]- 4-thiazolidone(sodium salt),

3-benzyl-2-phenylimino-5-o-sulfobeuzal-4-thiazolidone (sodium salt),

5 2,4-dicarb oxymethoxyb enzal) -3-phenyl-2-phenylimino- 4-thiazolidonesodium salt, etc.,

tartrazine, and the like filter dyes.

Hardening materials that may be used to advantage include such hardeningagents as formaldehyde; a halogensubstituted aliphatic acid such asmucobromic acid as described in White US. Patent 2,080,019, issued May11, 1937, a compound having a plurality of acid anhydride groups such as7,8-diphenylbicyclo (2,2,2)-7-octene'-2,3,5, 6-tetra-carboxylicdianhydride, or a dicarboxylic or a disulfonic acid chloride such asterephthaloyl chloride or naphthalene-1,5-disulfonyl chloride asdescribed in Allen and Carroll U.S. Patents 2,725,294, and 2,725,295,both issued Nov. 29, 1955; a cyclic 1,2-diketone such ascyclopentane-1,2-dione as described in Allen and Byers US. Patent2,725,305, issued Nov. 29, 1955; a bisester of methane-sulfonic acidsuch as 1,2-di(methanesulfonoxy) ethane as described in Allen and LaaksoUS. Patent 2,726,162, issued Dec. 6, 1955;1,3-dihydroxymethylbenzirnidazol-Z-one as described in July, Knott andPollak, US. Patent 2,732,316, issued J an. 4, 1956; a dialdehyde or asodium bisulfite derivative thereof, the aldehyde groups of which areseparated by 2-3 carbon atoms, such as B- methyl glutaraldehydebis-sodium bisulfite as described in Allen and Burness, Canadian Patent588,451, issued Dec. 8, 1959; a bis-aziridine carboxamide such astrimethylene bis(1-aziridine carboxamide) as described in Allen andWebster US. Patent 2,950,197, issued Aug. 23, 1960; or2,3-dihydroxydioxane as described in Jeffreys US. Patent 2,870,013,issued Jan. 20, 1959.

The photognaphic element utilizing my light-screening layers havelight-sensitive emulsion layers containing silver chloride, silverbromide, silver chlorobromide, silver iodide, silver bromoiodide, silverchlorobromoiodide, etc., as the light-sensitive material. Anylight-sensitive silver halide emulsion layers may be used in thesephotographic elements. The silver halide emulsion may be sensitized byany of the sensitizers commonly used to produce the desiredsensitometric characteristics.

In the accompanying drawing which further illustrates the preferredphotographic elements of my invention:

FIG. 1 shows light-screening layer 10 comprising gelatin, an acidsubstituted filter dye and the mordant of Example 1 coated over alight-sensitive silver halid emulsion layer 11 which is coated onsupport 12.

FIG. 2 shows antihalation layer 15 comprising gelatin, an acidsubstituted dye and the mordant of Example 1,

coated adjacent to support '16 and a light-sensitive silver halideemulsion layer 14 coated over layer 15.

FIG. 3 shows a multilayer color element comprising a support 21 having ared-sensitive silver halide emulsion layer 20 coated thereon, agreen-sensitive silver halide emulsion layer 19 coated over layer 20, alight-screening layer 18 comprising gelatin, an acid substituted dye,and the mordant of Example 1 coated over layer 19, and a blue-sensitivesilver halide emulsion layer 17 coated over layer 18.

The use of my alkali-release mordants in light-screening layers overlight-sensitive silver halide emulsion layers, and in antihalationundercoat layers, to produce improved photographic elements has beenillustrated in the preceding examples. However, it will be apparent thatthe mordants of the invention can also be advantageously used inlight-screening layers between two or more color sensitized silverhalide emulsion layers, or in antihalation backing layers, orincorporated directly in light-sensitive silver halide emulsion layers,or they can be used to prepare imbibition dye trapsfer blanks ofimproved properties.

The invention has been described indetail with particular reference topreferred embodiments thereof but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention as described 'hereinabove and as defined in the appendedclaims.

I claim:

1. A photographic element comprising a support material having thereon ahydrophilic colloid layer containing at least one mordant represented bythe formula:

wherein n represents an integer of from 1 to 2; g represents an integerof from 1 to 2; m1 represents an integer of from 1 to 2; R represents amember selected from the class consisting of a lower alkyl group, alower alkoxy group, an aryl group, an aryloxy group and an aralkylgroup; R represents a member selected from the class consisting ofhydrogen, an alkyl group, an aryl group, and when taken together withthe R group represents a divalent alkylene group having the formula:

wherein j represents an integer of from 3 to 4; R represents a memberselected from the class consisting of an alkyl group, an aryl group andwhen taken together with the R group represents the said divalentalkylene group, such that when R and R are taken together to form saiddivalent alkylene group, n and g each represent the integer 1; Rrepresents a member selected from the class consisting of hydrogen, analkyl group and an aryl group; R represents a member selected from theclass consisting of hydrogen, an alkyl group and an aryl group; when mrepresents the integer 2, A represents a bifunctional group having amolecular weight less than in which each of the said functional groupsis a substituted nitrogen atom having a valence with an odd number offrom 3 to 5 with none of the said substituents attached to nitrogenbeing hydrogen, and when the nitrogen atoms have a valence of 5, one ofsaid substituents on each of said nitrogen atoms is an acid anion, andwhen m represents the integer 1, A represents a substituted nitrogenhaving a valence having an odd number of from 3 to 5 with none of saidsubstituents attached to nitrogen being hydrogen, and when the nitrogenatom has a valence of 5, one of said substituents on the said nitrogenis an acid anion, said A group having a molecular weight of less than300, said element containing silver halide.

1 2. A photographic element of claim 1 in which when m is the integer 2,A represents a group selected from the class consisting of N group, a-NN- group and a N group Z X Z X R5 wherein R represents a lower alkylgroup; d represents an integer of from 2 to 6; X represents an acidanion; Z represents the nonmetallic atoms required to complete a nucleusselected from the class consisting of an imidazoline nucleus, abenzimidazoline nucleus and a naphthimidazoline nucleus; R represents agroup selected from the class consisting of an alkyl group, and an arylgroup; and when m is the integer l, A represents a group selected fromthe class consisting of group, aN-R group and a NCHRB group R6 X R7wherein R R and R each represents an alkyl group, and together R and Rrepresent the nonmetallic atoms required to complete a group selectedfrom the class consisting of piperidine, N-substituted piperazine, andmorpholine; R represents a member selected from the group consisting ofhydrogen, and a lower alkyl group; X represents an acid anion and Zrepresents the nonmetallic atoms required to complete a heterocyclicnucleus having from 5 to 6 members in the ring.

3. A photographic element of claim 1 in which when m is the integer 2, Arepresents a group selected from the class consisting of V aN a N N-group /I CHZ-CHZ X CH2 R4 OH: R;

R /R Z a N group, a NR group and a N CHR group R, X B

wherein R R and R each represents an alkyl group, and together R and Rrepresent the nonmetallic atoms required to complete a group selectedfrom the class consisting of piperidine, N-substituted piperazine, andmorpholine; R represents a member selected from the group consisting ofhydrogen, and a lower alkyl group; X represents an acid anion and Zrepresents the nonmetallic atoms required to complete a heterocyclicnucleus having from 5 to 6 members in the ring selected from the classconsisting of a thiazoline nucleus, a benzothiazoline nucleus, anaphthothiazoline nucleus, a thianaphtheno-7,6',4,S-thiazoline nucleus,an oxazoline nucleus, a benzoxazoline nucleus, a naphthoxazolinenucleus, a selenazoline nucleus, a benzoselenazoline nucleus, anaphthoselenazoline nucleus, a thiazoline nucleus, at 1,2,3,4-tetrahydroisoquinoline nucleus, a 3,3-dialkylindolenine nucleus, animidazoline nucleus, a benzimidazoline nucleus, and a naphthimidazolinenucleus.

4. A light-sensitive photographic element comprising a support materialhaving thereon a hydrophilic colloid layer container at least onesubstantially nonditfusible salt of a water-soluble acid dye with acompound represented by the formula:

wherein p represents an integer of from 1 to 3; R and R each representsan alkyl group, R and R taken together represent the nonmetallic atomsrequired to complete a group selected from the class consisting ofpiperidine, N-substituted piperazine and morpholine; and R represents amember selected from the class consisting of the hydrogen atom, an alkylgroup, an aryl group, an aralkyl group, an alkoxy group, an aryloxygroup, an alkoxyalkyl group, and an acylamino group; said compoundhaving a molecular weight of at least 300, said element containingsilver halide.

5. A light-sensitive photographic element comprising a support materialhaving thereon a hydrophilic colloid layer containing at least onesubstantially nonditfusible salt of a water-soluble acid dye with acompound represented by the formula:

( lah:

wherein p represents an integer of from 1 to 3, R R and R eachrepresents an alkyl group, R and R taken together represent thenonmetallic atoms required to complete a group selected from the classconsisting of piperidine, N-substituted piperazine and morpholine; Rrepresents a member selected from the class consisting of the hydrogenatom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group,an aryloxy group, an alkoxyalkyl group, and an acylamino group; and Xrepresents an acid anion; said compound having a molecular weight of atleast 300, said element containing silver halide.

6. A light-sensitive photographic element comprising a support materialhaving thereon a hydrophilic colloid layer containing at least onesubstantially nondiffusible salt of a water-soluble acid dye with3-lauroylaminol- (N,N-dimethyl-3-amino propiophenone hydrochloride, saidelement containing silver halide.

7. A light-sensitive photographic element comprising a support materialhaving thereon a hydrophilic colloid layer containing at least onesubstantially nondifiusible salt of a water-soluble acid dye with3-dodecylphenylcarbamylcarbonylethyl N,N dimethylamine hydrochloride,said element containing silver halide.

8. A light-sensitive photographic element comprising a support materialhaving thereon a hydrophilic colloid layer containing at least onesubstantially nondilfusible salt of a water-soluble acid dye with3-laurylbenzoylethyl- N-methyl-N-morpholinium iodide, said elementcontaining silver halide.

9. A light-sensitive photographic element comprising a support materialhaving thereon a hydrophilic colloid layer containing at least onesubstantially nondiffusible salt of a water-soluble acid dye with1,4-bis(3-laurylbenzoylethyl)-N,N-dimethylpiperazinium diiodide, saidelement containing silver halide.

10. A light-sensitive photographic element comprising a support materialhaving thereon a hydrophilic colloid layer containing at least onesubstantially nondiffusible salt of a water-soluble acid dye with6-(N,N-dimethylaminomethyl)-2-laury1cyclohexane hydrochloride, saidelement containing silver halide.

11. A light-sensitive photographic element comprising a support materialhaving thereon a hydrophilic colloid layer containing at least onesubstantially nondifrusible salt of a watersoluble acid dye withN-methyl-N,N-bis (3-laurylbenzoylethyl)amine hydrochloride, said elementcontaining silver halide.

12. A light-sensitive photographic element comprising a support materialhaving thereon a hydrophilic colloid layer containing at least'onesubstantially nondifiusible salt of a Water-soluble acid dye with1,5-bis(3-laurylbenzoylethyl) N,N'-dimethylpentamethylenediaminedihydrochloride, said element containing silver halide.

13. A light-sensitive photographic element comprising a support materialhaving thereon a 'hydrophilic colloid layer containing at least onesubstantially nondilfusible salt of a water-soluble acid dye withl,3-di(3-laurylbenzoylethyl)benzimidazolinium diiodide, said elementcontaining silver halide.

14. A light-sensitive photographic element comprising a support materialhaving thereon a hydrophilic colloid layer containing at least onesubstantially nondiffusible salt of a water-soluble acid dye withphytylethyl-N,N,N- trimethyl ammonium iodide, said element containingsilver halide.

15. An element comprising a support material having thereon ahydrophilic colloid layer containing at least one salt of an acid dyeand a mordant represented by the formula:

wherein represents an integer of from 3 to 4; R represents an integer offrom 1 to 2; m represents an integer of from 1 to 2; R represents amember selected from the class consisting of a lower alkyl group, alower alkoxy group, an aryl group, an aryloxy group and an aralkylgroup; R represents a member selected from the class consisting ofhydrogen, an alkyl group, an aryl group, and when taken together withthe R group represents a divalent alkylene group having the formula:

-([JH(CH2) -1 wherein i represents an integer from 3 to 4; R representsa member selected from the class consisting of an alkyl group, an arylgroup and when taken together with the R group represents the saiddivalent alkylene group, such that when R and R are taken together toform said divalent alkylene group, n and g each represent the integer 1;R represents a member selected from the class consisting of hydrogen, analkyl group and an aryl group; R represents a member selected from theclass consisting of hydrogen, an alkyl group and an aryl group; when mrepresents the integer 2, A represents a bifunctional group having amolecular weight less than in which each of said functional groups is asubstituted nitrogen atom having a valence with an odd number of from 3to 5 with none of the said substituents attached to nitrogen beinghydrogen, and when the nitrogen atoms have a valence of 5, one of saidsubstituents o neach of said nitrogen atoms is an acid anion, and when mrepresents the integer 1, A represents a substituted nitrogen having avalence having an odd number of from 3 to 5 with none of saidsubstituents attached to nitrogen being hydrogen, and when the nitrogenatom has a valence of 5, one of said substituents on said nitrogen is anacid anion, said A group having a molecular weight of less than 300,said element containing silver halide.

UNITED STATES PATENT OFFICE Patent No.

834 February 4 1969 Dugald A. Brooks It is certified that error appearsin the above identified patent and that said Letters Patent are herebycorrected as shown below:

Column 15, lines 44 through 47, the right-hand formula should appear asshown below:

Column 16, lines l9 p Column 17, lines lines 44 and 45 R represents an"o neach" should 38 through 43, that part of the formula reading shouldread 39 through 43 that part of the formula reading 3 should read(-CH=C)g cancel "j represents an integer of from 3 to 4 integer of from1 to Z Column 18, line 26 read on each Signed and sealed this 15th dayof September 1970 (SEAL) Attest:

EDWARD M.FLETCHER,JR. Attesting Officer WILLIAM E. SCHUYLER,Commissioner of Paten

1. A PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT MATERIAL HAVING THEREON AHYDROPHILIC COLLOID LAYER CONTAINING AT LEAST ONE MORDANT REPRESENTED BYTHE FORMULA: